Composition of matter

ABSTRACT

This invention relates to the compound 2-(3,4,4-trifluoro-3butenylthio)-4-methylthiazole which is effective as a nematocide.

United States Patent Brokke 0C!- 10, 1972 COMPOSITION OF MATTER [51]Int. Cl. ..C07d 91/60 72 Inventor; Mervin Brokke, Richmond Calif. [58]Md 0! Search .260/302 R [73] Assignee: gtaulgierz \(llhemical Company,New Prim Emminer A|ex Maze] or Assistant Examiner-Jose Tova: [22] Filed:Nov. 20, 1969 Att0rneyWayne C. Jaeschke and Edwin H. Baker 21 A l. N 877538 I pp 0 57 ABSTRACT Rehml Applicauon Data This invention relates tothe compound 2-(3,4,4- DIVISIO" 0f 490,664 p 27. 1u-ifluoto-IS-butenylthio)-4-methylthiazole which is ef- 3,5l3172-fective as a nematocide.

[52] US. Cl. ..260/302 R 1 Claim, No Drawings this invention relates tocompounds of the general formula wherein R is a member selected from thegroup consisting of chlorothiophenyl, thio-3,4,4-trifluoro-3-butenyl,2-thio-4,4,6-trimethyldihydropyrimidyl, Z-thiobenzoxazoyl,2-thiobenzothiazolyl, 2-thio-4-alkylthiazolyl, S- 3,4,4-trifluoro-3-butenyl)-ethylenebis(dithiocarbamoyl), thiobenzyl,thionaphthyl, phthalimido, dithio- 3,4,4-trifluoro-3-butenyl,thiopyridyl, N-thiazolidyl dione, and 5-thio-3-phenyl-l,2,4-thiadiazolyl.

The compounds herein contemplated can be prepared by various methods.One such general method of preparing the compound with bonding by meansof a thio group is the condensation of the appropriate thiol (R-Sl-l)and 3,4,4-trifluoro-3-butenyl bromide, usually in the presence of anorganic base, such as triethylamine. Similarly, compounds, whereinbonding is through a heterocyclic nitrogen condensation is accomplishedusing the appropriate sodium or potassium salt of the heterocyclicnitrogen containing compound and 3,4,4-trifluor0-3-butenyl bromide. Thereactions proceed readily in the liquid phase. The employment of aninert organic solvent is also useful, facilitating processing as well asagitation of the reactants. Temperatures that permit operation in theliquid phase and which are between room temperature and refluxtemperature of the solvent, if one is used, are employed. Preferably thereaction mixture is refluxed, usually at an elevated temperature.

It has been found that the compounds of the present invention areparticularly effective as nematocides. They are effective in the controlof nematodes when applied to a nematodal habitat.

The compounds of the present invention may be prepared in accordancewith the following illustrative examples.

EXAMPLE I Preparation of p-chlorophenyl 3,4,4-trifluoro-3-butenylsulfide.

In 200 ml. methanol was dissolved l4.4 g. of pchlorothiophenol. To thissolution was added 25 g. of 25 percent sodium methoxide followed by l8.9g. of 3,4,4-trifluoro-l-bromobutene 3. The resulting mixture was stirredand heated under reflux for l hour. The solvent was removed in vacuo.The residue was taken up in benzene, washed with water and dried overanhydrous magnesium sulfate. The benzene was evaporated. The wasobtained l9 3 g. of the title compound, n l.5360.

EXAMPLE 2 Preparation of Bis(3,4,4-trifluoro-3-butenyl)ethylene-bis(dithiocarbamate).

Ethylene diamine (0.2 moles) and triethylamine (02 moles) were dissolvedin l00 ml. of dioxane. Carbon disulfide (0.2 moles) was added dropwisewith stirring at 10 -20 C. Stirred at room temperature for 15 minutesafter addition was completed, then heated to 40 C. for [5 minutes. Tothe reaction mixture was added 0.15 mole (28.4 g.) of3,4,4-trifluoro-3-butenyl bromide. This was heated to 60 C. for 2 hours.The reaction mixture was poured into water and extracted with benzene.The benzene solution was subsequently washed with water, dried overanhydrous calcium chloride and finally the benzene removed in vacuo.There was obtained 77.4 g. of the title compound, n

EXAMPLE 3 Preparation of 3-Phenyl-5-(3,4,4-trifluoro-3-butenyl thia l,2,4-thiadiazole.

3-Phenyl-l,2,4-thiadiazole thiol-S, 6.6 g., were mixed with 9.5 g. of3,4,4-trifluoro-3-butenyl bromide in cc. of dioxane as solvent with l0.lg. of triethylamine as the catalyst. The reaction mixture was refluxedfor 2% hours. Isolation of the title compound was in the same manner asin Example 2. There was obtained 8.8 g. ofa dark oil, n 1.5687.

EXAMPLE 4 Preparation of N-(3,4,4-trifluoro-3-butenyl) 2,4-thiazolidenedione.

In I00 ml. of methanol there was dissolved l 1.7 g. of2,4-thiazolidinedione. This was treated with 0.1 mole of sodiummethoxide in methanol. To this solution was added l8.9 g. of3,4,4-trifluoro-3-butenyl bromide. The resulting mixture was refluxed 2hours. The solvent was then evaporated and the residue was taken up inbenzene. The benzene solution was washed with water, dried overanhydrous calcium chloride, and the solvent evaporated. There wasobtained 7.2 g. of the title compound, n 1.4678. Analysis of theinfrared spectrum supported the proposed structure.

As previously mentioned, the herein described novel compositionsproduced in the above described manner are biologically active compoundswhich are useful and valuable in the control of various organisms. Thecompounds of the invention were tested as nematocides in the followingmanner.

Nematocide Evaluation Test. This test determines a candidates action onroot-knot nematodes (Meloidogyne, sp.) in soil. One-pound portions ofsoil infested with root-knot nematodes were placed in quart jars. Thechemical to be tested was pipetted into the nematode-infested soil atvarious dilutions of from 55 to 1 part per million (ppm) or untilactivity was lost. After mixing the candidate compound into the soil,the soil was sealed for 48 hours. The treated soil was then placed inpaper containers and allowed to stand in a greenhouse one week forairing. At the end of this time a tomato plant was transplanted into thesoil. The rootknot nematodes attack the tomato plant roots if theysurvived the chemical treatment, and cause swelling or knots on theroots. Four weeks after treatment the plant was removed from the soiland the roots inspected. The lowest concentration which preventednematode development was recorded.

The following table is a listing of the compounds prepared according tothe aforedescribed procedures. Column ll is the results obtained fromthe nematocide evaluation test. The values given in Column ll areconcentrations (ppm) which allowed no nematode development.

TABLE Col. 1 Col. 11

Nematode Compound n Control (pp p-chlorophenyl 3,4,4-trifluoro-3-butenylsulfide 1.5360 50 bis(3,4,4-trifluoro-3-butenyl) sulfide 1.4087 2.5 2-(3,4,4-trifluoro-3-butenylthio )-4,4,6-

trimethyldihydropyrimidine 1.4949 25 2-(3,4,4-trifluoro-3buteny1thio)-benzoxazole 1.5385 (2.5) 2-(3,4,4-trilluoro-3-butenylthio)-benzo iazole1.5863 (2.5) 2-(3,4,4-trifluoro-3-butenylthio)-4 methylthiazole 1.5358(I) bis( 3,4,4-trifluoro-3-butenyl) ethylenebis(dithiocarbamate) 1.5292phenyl 3,4,4-trifluoro-3-butenyl sulfide- 1.5442 503-phenyl-5-(3,4,4-trifluoro-3-butenylthia)-l,2,4-thiadiazole 1.5687(2.5) 3,4,4-trifluoro-3-butenyl benzyl sulfide 1.5120 253,4,4-triflu0ro-3-butenyl a naphthyl sulfide 1.5805 (50)N-(3,4,4-triflu0ro-3-butenyl)phthalimide (semi- (2.5)

solid) bis( 3,4,4-tril'luoro-3-butenyl) disulfide (liquid) (2.5) 2(3.4,4-tril'luoro-3-butenylthio)- pyridine 1.5258 25 4J.4,4-trifluoro-3-butenylthio idine 1.5471 (2.5)

thiazolidenedione [.4678 (l) partial control The compounds of thepresent invention may be used as effective nematocides and may beapplied in a variety of ways at various concentrations. In practice thecompounds are usually formulated with an inert nematocidal adjuvant,utilizing methods well-known to those skilled in the art, thereby makingthem suitable for application as dusts, sprays, or drenches. The amountapplied will depend upon the nature of the nematode to be controlled andthe rate of application may vary from 1 to 50 pounds per acre. Oneparticularly advantageous way of applying the nematocidal compositioncomprising the adjuvant and an effective amount of a compound of thepresent invention is a spray, drench or dust followed by incorporation.

Various changes and modifications may be made without departing from thespirit and scope of the invention described herein as will be apparentto those skilled in the art to which it pertains. It is accordinglyintended that the present invention shall only be limited by the scopeof the appended claims.

We claim:

1. The compound, thio)-4-methylthiazole.

2-( 3,4,4-trifluoro-B-butenyl-

